Acetylene peroxides



Patented Feb. 23, 1954 UNITED STATES PATENT OFFICE 2,676,384 v ACETYLENE PEROXIDES ,Nicliolas ,lilelmont, Mass., assignor Research CO PDration, New York, N-.YI,'- a, corporation of New York No Drawing. Application Septemlier 24, I951)" Serial No. 248,090

w intention id as, to a etylene, peroxides oxide (V) witht- -butyl alcohol is-giyen by Edna and to' methods for making them. tion 4. v

Acetylene peroxides of the type described here- (4) in have not heretofore been known and it could a R R R not be predicted whether they would be stable 2 c 1 (CHmCOHI'm enough to isolate. It is now possible to produce OOH OOH R m them in good yield'by' the methods oithe invenv 1. tion and it is'found that they are unusually stable I I in spite of the presence of acetylene groups in v o 0 '1 their molecules. I I g e ;c o he g The peroxides of the invention may be prer pared by allowing an acetylene carbinol (I) in V which R1 and R2 are hydrocarbon radicals or an acetylene glycol (IV) in which R1 and R2 also represent hydrocarbon radicals to react with hy- '5 drogen peroxide at temperatures between 10 and .C. in' the presence of mineral acids such as sulfuric and phosphoric acids to producethe acetylen hy q e id s o th typ s (I o respectively, and in the case of acetylene carbinols 0 t The acetyleneperoxides of the present invention are useful forthe synthesis. of other useful organic compounds, as polymerizing catalysts in emulsions as ,:well as in single phase systems," as bleaching agents and as germicids The principlesof the invention are illustrated bythe-following specific examplesz' also the peroxide (III) I 'he reactions are illus- I trated by Equations 1 and 2: B-methyl-3-figjclroperoiiypentyne-l (1 To a CO1d".mlXturei(-0-C.) of='30 .6"g'. of 1 Z E H+ H OH+ H+ 5 hydrogenn eroxide and 18 en of 95.5%..sulf uric I so and \d. dropwise with, rapid stirring. 20 g. 03 (I) 1 .e

05011 or 3-methyl-3-hydro xypentyne-1 R|B2C-OECH+ Rant-o 4 31120 (CHICHZGKGEPCEOH 00H RlR5C-0 O I H H (11 EOE ath sours f.abdu on e l ho r l mr (In) perature of the .miXtufeshould not be. allowedto rise, above 5f C during, the ,initial' stages oilthe V reactionl S irringf', i's conti nued",, for 4.5; hours R1R2GCECCR1R2 2110 OH+ H+ lqn'g than tune is diluted with an equal (311 I OH of pir ted, mmon um sulfate? solution I .7 actedwith ,et a rrhe ether extractlis Rlmc-ozo cRrRz l z'rho' shaken with ,solid magnesiumrcarbonate. to re.-

.5 3 moyetracesoi sulfuric acid thendried over ma'g 5 nesium sulfate, filtered and the ether removed under reduced pressure; yield, 22 g. (94% of The peroxide (III) may also be prepared by theory) ot material active oxygeneontent allowing an equimole cular mixture of the hydro- 0f '-9% corresponds to' 85% Of "3- y Y- peroxide (II) and the carbinol (I) to react at dropero yp y 0' p yt u t' low temperatures in the presence of a mineral 4 fractionated under'reduced pressure and-the fracacid-as illustrated by'Equationfi. tion; boiling."38-40 C.;-(5 mm.) is. collected; v 71. 53 1.4396; d42 0.9547. MRn (calcd), 31:63; M v n MRD obscr r31e2Lv .o V Y Y I K310435011 H+ I .Di-(3-nithylpentynyl)-3-peroxide is also pro- H 0H 5 duced.

V CECE 050E 2 h H10 pswam-amideemanates- These p rq de n s wb l s at 9r e r ,Us ifig t jehie teehriiqoeeiidlufltiertii sane fl mmorthe aim-anon cree er n conditions-es thoseof Examplell 20 g. of 3;

methyl-3-hydroxybutyne-1 is allowed to react with a mixture of 35.44 g. of 50% hydrogen peroxide and 55.7 g. of 95.5% sulfuric acid. A yield of 23.3 g. (99.5% of theory) of crude product is obtained analyzing 80% of the hydroperoxide. This is further purified by distillation under reduced pressure and the fraction boiling at 40-42 C. (17 mm.) collected; n 1.4289; d4 0.945. MR1) (calcd), 27.01. MR1: (obsd.) 27.26.

The corresponding diacetylene peroxide is also formed.

EXAMPLE 3 2,5-dz'methyl-2,5-dihydroperoxyheryne-3 Using the same technique as that used in Examp e 1, 50 g. of 2,5-dimethyl-2.S-dihydroxyhexyne-3 (added in small portions in the course of one hour) is allowed to react with a mixture (maintained at -4 to l C.) of 52.5 g. of 50% hydrogen peroxide and 69 g. of 95.5% sulfuric acid. A yield of 52 g. (85% of theory) of solid product is obtained having a purity of 92%. This is recrystallized from benzene, M. P. 107-l09 C. (decompn).

EXAMPLE 4: 1,1'-dz'hydroperoa:y-1,1 -dz'cyclohemylacetylene The dihydro eroxide of dicyc ohexyl acety ene glycol is prepared in exactly the same manner as in Example 1. 1.1'-dihvdroxv-1.1'-dicyclohexylacetylene 10 g.) is slowlv added with ra id stirrin to a mixture (maintained at C.) of 9.6 g. of 50% hvdro en peroxide and 14 of 95.5% sulfuric acid. Aft r four hours of stirring. the mixture is di uted with an ecual volume of saturated sol tion of ammon um sulfate and extracted with ether. From the ether extract is Ohtained 9 a. of solid pro uct having a urity of 85%. This is recrystallized from cyclohexane; M. P. 95 C. (decompn.).

EXAMPLE 5 Di- (3-methylbutynyl) -3-pero:rzcle To 12.7 g. of 70% sulfuric acid maintained between 3 and 0 C. was added dr o ise with rapid stirring a mixture of 6.05 g. of 3-methvl-3- hydro eroxvbutvne-l (pr pared un er Example 2) and 5.07 g. of 3-methvl-3-hydrnxvhntvne1 in the course of one-ha f hour. Stirrina is con-- tinued at 0 C. for 4.5 hours lon er: then t e mixture is diluted with two volumes of water and extracted with low boiling petroleum ether. The petroleum ether extract is shaken with two nortions of sodium hydroxide to remove the unus d hv r nero ide. washed with water and dried. Finall the petr leum ether is removed. the residue distilled un er red ced presure and the portion boiling at 60 C. ('76 mm.) collected.

EXAMPLE 6 2,5-dimethyl-2,5-di(t-butylperomy) -hexyne-3 To a cold mixture (0 C.) of 6 g. of t-butyl alcohol and 11.2 g. of 70% sulfuric acid is slowly added with stirring 4.7 g. of 2,5-dimethyl-2,5-dihydroperoxyhexyne-3 in the course of minutes. The mixture is then allowed to stir at room temperature for five hours; then diluted with two volumes of water and extracted with ethyl ether. The ether solution is washed with water, dried and the ether removed. A yield of 6.8 g. (88.3% of theory) is obtained. The peroxide is distilled under reduced pressure and thefraction boiling at es-s'rc. (2 -mm.) cqllectedg va 0-0502! R2 $OE wherein R1 and R2 are hydrocarbon radicals.

4. Acetylene peroxides of the general formula cozon Rz )OH wherein R1 and R2 are alkyl radicals.

5. Acetylene peroxides of the general formula wherein R1, R2, R3 and R4 are hydrocarbon radicals.

6. Acetylene peroxides of the general formula wherein R1, R2, R3 and R4 are alkyl radicals.

7. Acetylene peroxides of the general formula wherein R1, R2, R3 and R4 are hydrocarbon radicals and R5 and Rs are selected from the group consisting of hydrogen and hydrocarbon radicals.

8. Acetylene peroxides of the general formula wherein R1, R2, R3 and R4 are hydrocarbon radicals.

9. Acetylene peroxides of the general formula wherein R1, R2, R3 and R; arealkyl radicals.

10. A method of making acetylene peroxides which comprises reacting at a temperature not exceeding about 20 C. in the presence of a mineral acid hydrogen peroxide and an acetylene carbinol of the general formula wherein R1 and R2 are hydrocarbon radicals and R3 is selected from the group consisting of hydrogen and hydrocarbon radicals.

11. A method of making acetylene peroxides which comprises reacting at a temperature not exceeding about 20 C. in the presence of a mineral acid hydrogen peroxide and an acetylene carbinol of the general formula wherein R1 and R2 are alkyl radicals.

12. A method of making acetylene peroxides which comprises reacting at a temperature not exceeding about 20 C. in the presence of a mineral acid hydrogen peroxide and an acetylene carbinol of the general formula wherein R1, R2, R3 and R4 are alkyl radicals.

NICHOLAS A. MILAS.

References Cited in the file of this patent UNITED STATES PATENTS .Name Date Rust et al July 25, 1950 OTHER REFERENCES Piganiol, Acetylene Homologs and Derivatives 121 H22 (1950).

Number 

1. ACETYLENE PEROXIDES CHARACTERIZED BY HAVING AT LEAST ONE TERTIARY CARBON ATOM HAVING A PEROXY GROUP AND AN ACETYLENIC GROUP ATTACHED THERETO
 10. A METHOD OF MAKING ACETYLENE PEROXIDES WHICH COMPRISES REACTING AT A TEMPERATURE NOT EXCEEDING ABOUT 20* C. IN THE PRESENCE OF A MINERAL ACID HYDROGEN PEROXIDE AND AN ACETYLENE CARBINOL OF THE GENERAL FORMULA 